Flexible substrates containing a radiation curable coating composition

Abstract

A radiation curable coating comprising: A. an oligomer of Formula I: <IMAGE> (I) wherein: R1 is hydrogen or methyl; Y is a divalent urethane residue; B. an acrylic ultra-violet light absorber of Formula IV: <IMAGE> (IV) wherein R4 is alkyl or hydroxy alkylene. Preferably the coating composition contains a vinyl monomer copolymerizable with the oligomer. The process for curing the coating is also disclosed.

What is claimed is: 
     
       1. A laminate comprising a planar sheet of clear polyvinyl chloride with a film coating 0.1 to 10 mils in thickness comprising an acryl urethane oligomer represented by the formula: ##STR8## wherein R 1  is hydrogen or methyl; Y is a divalent urethane residue and an acrylic ultra-violet light absorber of Formula IV: ##STR9## wherein R 4  is alkyl or hydroxy alkylene. 
     
     
       2. A radiation curable coating composition comprising: A. an oligomer of Formula I: ##STR10## wherein: R 1  is hydrogen or methyl; Y is a divalent urethane residue; B. an acrylic ultra-violet absorber of Formula IV: ##STR11##  wherein R 4  is alkyl or hydroxy alkylene.   
     
     
       3. The coating composition of claim 2, further comprising a vinyl monomer selected from the group consisting of N-vinyl-2-pyrrolidone, acrylic acid esters and mixtures thereof. 
     
     
       4. The coating composition of claim 2 further comprising an addition polymerization inhibitor present in an amount sufficient to avoid the auto-polymerization of the composition during storage. 
     
     
       5. The coating composition of claim 4 wherein the addition polymerization inhibitor is present in an amount from 100-300 PPM weight percent based upon the weight of the composition. 
     
     
       6. The coating composition of claim 2 further comprising a surfactant. 
     
     
       7. The coating composition of claim 6 wherein the surfactant is present in an amount from 0.1 to 5 weight percent based upon the weight of the composition. 
     
     
       8. The coating composition of claim 6 wherein the surfactant is a silicone surfactant. 
     
     
       9. The coating composition of claim 3 wherein the weight ratio of oligomer to vinyl monomer is from 1:9 to 9:1. 
     
     
       10. The coating composition of claim 2 further comprising a photo-initiator present in an amount sufficient to initiate the desired polymerization under the influence of the amount of actinic light energy absorbed. 
     
     
       11. The coating composition of claim 10 wherein the photo-initiator is present in an amount from 0.01 to 5 weight percent based upon the weight of the composition. 
     
     
       12. The coating composition of claim 2 wherein the acrylic ultra-violet light absorber is present in an amount from 0.5 to 3 weight percent based on the weight of the composition. 
     
     
       13. A coating composition of claim 2 which is photopolymerizable in the presence of ultra-violet light to produce an adherent coating that is weather-resistant, flexible, scratch-resistant, stain-resistant, abrasion-resistant, and solvent-resistant, said coating composition consisting essentially of: A. an oligomer of Formula II: ##STR12##  wherein: R 1  is hydrogen or methyl; R 2  is lower alkylene;   R 3  is aliphatic or cycloaliphatic;   X is --O-- or --NH--;   n is an integer from 2 to 50 inclusive;     B. N-vinyl-2-pyrrolidone;   C. 1-4 butanedioldiacrylate;   D. ethyl-2-cyano-3,3-diphenyl acrylate present in an amount from 0.5 to 3 weight percent based on the weight of the composition;   E. a photo-initiator present in an amount from 0.01 to 5 weight percent based on the weight of the composition;   F. an addition polymerization inhibitor present in an amount from 100-300 PPM based on the weight of the composition;   G. a silicone surfactant present in an amount from 0.1 to 5 percent based on the weight of the composition, wherein the ratio A:B is from 1:3 to 3:1; and   wherein the ratio A:C is from 1:3 to 3:1.     
     
     
       14. A coating composition of claim 2 which is photopolymerizable in the presence of ultra-violet light to produce an adherent coating that is weather-resistant, flexible, scratch-resistant, stain-resistant, abrasion-resistant, and solvent-resistant, said coating composition consisting essentially of: A. an oligomer of Formula III: ##STR13##  wherein: R 1  is hydrogen or methyl; R 2  is lower alkylene;     
     
     
       R 3  is aliphatic or cycloaliphatic; X is --O-- or --NH--;   n is an integer from 2 to 50 inclusive;   B. N-vinyl-2-pyrrolidone;   C. 1-4 butanedioldiacrylate;   D. ethyl-2-cyano-3,3-diphenyl acrylate present in an amount from 0.5 to 3 weight percent based on the weight of the composition;   E. a photo-initiator present in an amount from 0.01 to 5 weight percent based on the weight of the composition;   F. an addition polymerization inhibitor present in an amount from 100-300 PPM based on the weight of the composition;   G. a silicone surfactant present in an amount from 0.1 to 5 percent based on the weight of the composition, wherein the ratio A:B is from 1:3 to 3:1; and   wherein the ratio A:C is from 1:3 to 3:1.     
     
     
       15. The radiation curable coating composition of claim 2 wherein said acrylic ultra-violet absorber is ethyl-2-cyano-3, 3-diphenyl acrylate present in an amount from 0.5 to 3 weight percent based on the weight of the coating composition. 
     
     
       16. The radiation curable coating composition of claim 2, further comprising a photo-initiator present in an amount from 0.01 to 5 weight percent based on the weight of the coating composition. 
     
     
       17. A coating composition of claim 2 which is photopolymerizable in the presence of ultra-violet light to produce an adherent coating that is weather-resistant, flexible, scratch-resistant, stain-resistant, abrasion-resistant, and solvent-resistant wherein said oligomer of Formula I is an acryl urethane of Formula III: ##STR14## wherein: R 1  is hydrogen or methyl; R 2  is lower alkylene;   R 3  is aliphatic or cycloaliphatic;   X is --O-- or --NH--;   n is an integer from 2 to 50 inclusive and further comprising a photopolymerizable vinyl monomer selected from the group consisting of N-vinyl-2-pyrrolidone, acrylic acid esters and mixtures thereof; and a photo-initiator present in an amount from about 0.01 to 5 weight percent based on the weight of the composition.     
     
     
       18. A coating composition of claim 2 which is photopolymerizable in the presence of ultra-violet light to produce an adherent coating that is weather-resistant, flexible, scratch-resistant, stain-resistant, abrasion-resistant, and solvent-resistant wherein said oligomer of Formula I, is an acryl urethane of Formula II: ##STR15## wherein: R 1  is hydrogen or methyl; R 2  is lower alkylene;   R 3  is aliphatic or cycloaliphatic;   X is --O-- or --NH--;   n is an integer from 2 to 50 inclusive; and further comprising a photpolymerizable vinyl monomer selected from the group consisting of N-vinyl-2-pyrrolidone, acrylic acid esters, and mixtures thereof; and a photo-initiator present in an amount from 0.01 to 5 weight percent based on the weight of the composition.     
     
     
       19. A laminate comprising a planar sheet of polycarbonate with a film coating 0.1 to 10 mils in thickness comprising an acryl urethane oligomer represented by the formula: ##STR16## wherein R 1  is hydrogen or methyl; Y is a divalent urethane residue and an acrylic ultra-violet light absorber of Formula IV: ##STR17## wherein R 4  is hydroxy alkylene.